Polymers comprising phosphorus atoms in the polymer backbone are desirable for a variety of applications, including use as polymeric supports for metal catalysts (i.e. Peckham, T. J., et al. (1999) Macromolecules 32:2830-37). Synthetic approaches to the production of such polymers have included ring-opening polymerization (i.e. Peckham, T. J., et al. [supra]; and Kobayashi, S., et al. (1984) Macromolecules 17:107-115), condensation or co-polymerization of aryl phosphines with alkyl radicals and alkylene moieties (i.e. Fox, M. A., et al. (1991) Macromolecules 24:4626; Lucht, B. L. and St. Onge, N. O. (2000) Chem. Commun. 2000:2097-8; Kanazawa, A., et al. (1993) J. of Polymer Science 31:3031-38; and JP6016508). These approaches have resulted in the production of oligomers or polymers of unspecified length comprising phosphine or phosphonium moieties in a chain which otherwise contains aryl groups and/or alkyl or alkene spacers. None of these approaches allow for the production of polymers containing C—P bonds and approximately equimolar amounts of carbon and phosphorus atoms in the polymer backbone.
It has been reported that unstable phosphaalkenes such as methylenephosphine can spontaneously polymerize into unspecified oligomers or polymers (Klebach, T. C., et al. (1978) J. Am. Chem. Soc. 100:4886-8; Pellerin, B., et al. (1987) Tetrahedron Letters 28:5811; Quin, L. D., et al. (1987) Tetrahedron Letters 28:5783-86; Chow, J. R. and Goldwhite, H. (1989) J. Phys. Chem. 93:421-6; and Gaumont, A. C., et al. (1994) J. Chem. Soc. Chem. Commun. 945-6; and Aitken, R. A., et al. (1997) Tetrahedron Letters 38:8417-20). In view of the instability of acyclic compounds containing carbon-phosphorus π bonds, researchers have focused on the development of thermally stable phosphaalkenes, phosphaallenes and phosphaalkynes which have been kinetically stabilized through the presence of bulky substituents on the phosphorus atom (i.e. Gaumont, A. C. and Denis, J. M. (1994) Chem. Rev. 94:1413-39). One of the first such thermally stable phosphaalkene with a localized P═C bond was P-mesityldiphenylmethylenephosphine, the structure of which is shown below in which Ph is phenyl and Mes is 2,4,6-trimethylphenyl (Klebach, T. C., et al. [supra]; Van der Knapp, T. A., et al. (1984) Tetrahedron 40:765-5; and Mundt, O., et al. (1986) Z. Anorg. Allg. Chem. 540/541:319-35).

Various thermally stable acyclic phosphaalkenes have been synthesized and reported (i.e. Appel, R. (1990) “Multiple Bonds and Low Coordination in Phosphorus Chemistry”, Chapter 4; M. Regits and O. J. Scherer (eds), Thieme; Stuttgart) but there have been no reports of their use in polymerization reactions.